Stereochemistry of mono- and dinuclear complexes of rhodium, iridium and ruthenium bearing bis(diphenylphosphinomethyl)phenylphosphine

Kosaka, Yosuke; Shinozaki, Yuichi; Tsutsumi, Yoshihiro; Kaburagi, Yoshihiro; Yamamoto, Yasuhiro; Sunada, Yusuke; Tatsumi, Kazuyuki

doi:10.1016/s0022-328x(03)00096-2

Cited by 15 publications

(4 citation statements)

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“…In addition, heterometallic complexes containing gold and iridium or gold and ruthenium with similar patterns, but with two different metal centers, have been described and their luminescent properties also studied. The fluxional behavior in solution of compound [Au 2 (TP) 2 ] 2þ has been studied by NMR [245,[342][343][344][345][346][347][348][349][350][351][352][353][354].…”

Section: Complexes With Bridging Bidentate Ligandsmentioning

confidence: 99%

Gold–Gold Interactions

Crespo

2008

Modern Supramolecular Gold Chemistry

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This chapter focuses mainly on closed shell gold(I) atoms which are found to feel attraction among themselves. This attraction is able to modify expected geometries or support one-, two-or three-dimensional arrays and also leads to interesting properties. Closed shell metal cations are expected to repel each other. Nevertheless, an important number of examples containing [d 8 -d 10 -s 2 ] interactions are known. Particularly strong evidence has been accumulated on the attraction between two or more d 10 shells. In the case of gold(I) such attraction between two or more monovalent gold(I) ions in compounds has been observed structurally for a long time. In these situations the gold centers approach each other to a distance of between 2.7 and 3.3 Å. This range includes the distance between gold atoms in gold metal and approaches, or even overlaps with the range of distances found in the few real Au-Au single bonds. Schmidbaur coined the name aurophilic attraction in 1990 and defined it as the unprecedented affinity between gold atoms even with closed-shell electronic configurations and equivalent electrical charges [1]. Since that moment, aurophilicity has become one of the hot topics in gold chemistry, at first with the aim of understanding such interaction, more recently because of the observation that it may play an important role in interesting properties, thus understanding and modulating aurophilic interactions could help to govern these properties, which include the optical behavior. Although different origins are possible for the luminescent emissions of coordination complexes, such as intraligand transitions (ILT), ligand to metal or metal to ligand charge transfer transitions (LMCT, MLCT) and metal centered (MCT) transitions, in many luminescent gold complexes the emissions have been related to the presence of aurophilic interactions.Information about aurophilicity and chemical situations in which it is observed may be found in different works that may be classified as those which analyse closed shell interactions in general [2], those focused on aurophilicity [1,3], and others which analyze the role of these interactions in coordination [4] and organometallic gold Modern Supramolecular Gold Chemistry: Gold-Metal Interactions and Applications. Edited by Antonio Laguna

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Section: Complexes With Bridging Bidentate Ligandsmentioning

confidence: 99%

Gold–Gold Interactions

Crespo

2008

Modern Supramolecular Gold Chemistry

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“…Exploring tunable assemblages of heterodinuclear and heteromultinuclear complexes would be thus an important subject and has closely been indebted to designing metal supporting ligands. Among a number of polydentate ligands used to stabilize multimetallic systems, di- and tridentate phosphines, including bis(diphenylphosphino)methane (dppm) and bis[(diphenylphosphino)methyl]phenylphosphine (dpmp), have widely been used to create metal–metal-bonded homo- and heteromultinuclear structures. ,− In general, polyphosphine ligands possess the potential ability to organize heteromultimetallic centers because their variation of denticity may generate uncoordinated dangling phosphorus atoms capable of trapping additional metals; however, polyphosphines containing more than three P atoms have still been limited, owing to their synthetic difficulty and complicated stereoisomerism. − Recently, we have prepared a methylene-bridged linear tetraphosphine ligand, meso -bis[((diphenylphosphino)methyl)phenylphosphino]methane (dpmppm), and demonstrated that it effectively stabilized versatile tetrametallic chains of group 11 metal ions . Two dpmppm ligands assembled four Au I ions in a syn arrangement with respect to the bent Au I 4 string, and the flexible tetragold(I) chain {Au 4 (μ-dpmppm) 2 } 4+ incorporated a counteranion (X) in its bent pocket to afford {[Au 4 (μ-dpmppm) 2 ]X} 3+ (X = PF 6 , Cl) adducts, the structures of which varied depending on the trapped anions and modulated their intriguing luminous properties .…”

Section: Introductionmentioning

confidence: 99%

Heterotrinuclear Complexes with Palladium, Rhodium, and Iridium Ions Assembled by Conformational Switching of a Tetraphosphine Ligand around a Palladium Center

et al. 2011

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Reaction of [PdCl 2 (cod)] with a tetraphosphine, meso-bis[((diphenylphosphino)methyl)phenylphosphino]methane (dpmppm), afforded the mononuclear Pd II complexes [PdCl(dpmppm-κ 3 )]X (X = Cl (1a), PF 6 (1b)); the pincer-type dpmppm ligand coordinates to the Pd atom with two outer and one inner phosphorus atom to form fused six-and four-membered chelate rings. The remaining inner phosphine is uncoordinated and readily reacts with [Cp*MCl 2 ] 2 to give the heterodimetallic complexes [PdCl-(Cp*MCl 2 )(μ-dpmppm-κ 3 ,κ 1 )]X (X = Cl, M = Rh (21a), Ir (21b); X = PF 6 , M = Rh (23a), Ir (23b)). Attachment of the second metal fragment to the uncoordinated phosphine caused a crucial conformational change of the six-membered chelate ring from a stable chair conformation to a twist-boat structure, which concomitantly destabilizes the four-membered ring for its opening reactions. Complexes 21 (X = Cl) were converted to [PdCl 2 (Cp*MCl 2 )(dpmppmO)], in which the terminal P atom is dissociated and oxidized as Ph 2 P(O)CH 2 P(Ph)CH 2 P(Ph)CH 2 PPh 2 (dpmppmO), and in the presence of another 1 equiv of [Cp*M′Cl 2 ] 2 , complexes 21 were readily transformed into the heterotrinuclear complexes [PdCl 2 (Cp*M′Cl 2 )(Cp*MCl 2 )(μdpmppm-κ 2 ,κ 1 ,κ 1 )] (M = M′ = Rh (31a), Ir, (31b); M = Ir, M′ = Rh (31c)), where the third metal M′ is trapped by the terminal P atom with its four-membered-ring opening. Complexes 23 also reacted with another 1 equiv of [Cp*M′Cl 2 ] 2 to afford the heterotrinuclear complexes [PdCl(μ-Cl)(Cp*M′Cl)(Cp*MCl 2 )(μ-dpmppm-κ 2 ,κ 1 ,κ 1 )]PF 6 (M = M′ = Rh (32a), Ir, (32b); M = Ir, M′ = Rh (32c), M = Rh, M′ = Ir (32d)); the additional metal M′ is ligated by the terminal phosphine and is further connected to the Pd atom via a chloride bridge, resulting in a rather electron-deficient M′ center on the basis of cyclic voltammetry. These results exhibited that the addition of a bulky metal fragment to the uncoordinated phosphine of 1 brings about a conformational switch around the Pd center to promote the ring-opening reaction of the four-membered chelate ring, which leads to an incorporation of the third metal fragment to construct heterotrinuclear structures.

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“…This polymer is very easy to react with other ligands to form mononuclear or binuclear complexes. Because these complexes are generally excellent hydrogenation catalysts for unsaturated organic compounds [2][3][4][5][6][7][8][9], the reactions of [RuCl 2 (g 6 -C 6 H 6 )] x with a variety of monodentate nucleophiles and bidentate phosphine have been an active research area [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29]. Treatment of [RuCl 2 (g 6 -C 6 H 6 )] x with monodentate nucleophiles (tertiary phosphine, pyridine, tertiary arsine, etc.)…”

Section: Introductionmentioning

confidence: 99%